EP3402332A1 - Aqueous dispersions containing aclonifen and flufenacet - Google Patents

Abstract

The present invention relates to formulations in the form of aqueous dispersions comprising aclonifen and flufenacet, a mixture of anionic surfactants from the group of naphthalene sulfonates or from the group of condensation products of naphthalene sulfonates with formaldehyde, nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides, a specific mixture of organic and inorganic thickeners, to which optionally further agrochemical active substances and other usual adjuvants and additives may be added. The aqueous dispersions have a high storage stability and are suitable in the field of plant protection.

Description

 Aqueous dispersions containing aclonifen and flufenacet

Description The present invention relates to the field of crop protection formulations. In particular, the invention relates to formulations in the form of aqueous dispersions which contain the herbicidal active ingredients aclonifen and flufenacet and are stable on storage after replacement of tristyrolphenol ethoxylates in the formulations. Herbicides are generally not used in their pure form. Depending on the field of application and the type of application, as well as on physical, chemical and biological parameters, the active ingredients are used in admixture with customary auxiliaries and additives as active substance formulation. The combinations with other active ingredients for extending the spectrum of activity and / or for the protection of the crop plants (for example by safeners, antidotes) are also known.

Formulations of herbicidal active ingredients should generally have high chemical and physical stability, good applicability and ease of use, and a broad biological activity with high selectivity.

Aqueous dispersions for herbicidal active ingredients, which include aqueous suspension concentrates (SC), are known, i.a. from EP-A-0514768 (US 5,707,926), EP-A-0592880 (US 5,376,621) or WO 2007/112834 A2 which discloses formulations for flurtamones and diflufenican mixtures. The herbicidal active ingredients Aclonifen and Flufenacet are used alone and as a mixture (in a tank mix), inter alia, as aqueous suspension concentrates (SC), for example under the trade name Bandur 600 SC (Aclonifen) and Cadou 508 SC (Flufenacet). In addition, other mixing partners can be added, such as Brodal 500 SC (Diflufenican).

Disadvantage of the individual formulations underlying these or similar products is often their lower biological activity compared to so-called co-formulations (syn .: combination formulation, co-formulations, ready-to-use mixtures), in which several active substances in the fixed mixture Ratio in a formulation.

However, in high loaded co-formulations with multiple drugs, the

Stability requirements of each individual drug are taken into account, which may vary greatly depending on the active ingredient. In special cases, interactions can also be observed, such as the decomposition of one drug due to the direct presence of another. A particular problem is also the instability of formulations during storage, which reduces the shelf-life. Bearing instability is recognizable, for example, by the formation of a sediment (often due to crystal growth of an active ingredient), which not only greatly reduces the biological effectiveness of the individual active ingredients, but also their distribution in the field application is uneven. This leads, among other things, to areas of under-dosing, in addition to over-dosing areas where crop damage occurs, where the

unwanted growth of harmful plants is no longer adequately controlled. In addition, sub-doses in subsequent years can also lead to drug-resistant harmful plants. For example, here the field foxtail (Alopecurus myosuroides, ALOMY) should be mentioned, whose difficult combat u.a. in grain is a big problem.

A specific disadvantage of the above-mentioned Aclonifen SC formulations is the fact that they contain surfactants from the group of tristyrolenol ethoxylates (TSP-EO) which have a delayed biodegradability. In addition, TSP-EO contains free phenol as an undesirable secondary component, which has led to the inclusion of this group of compounds in the REACH substitution list (European Chemicals Regulation REACH: Registration, Evaluation, Authorization and Restriction of Chemicals).

 In attempts to prepare SC-Co formulations for the active ingredient mixture Aclonifen and Flufenacet, it came from Aclonifen SC formulations containing TSP-EO

unwanted effects. The addition of flufenacet resulted in a heavy sediment, which showed that formulations can not be produced on this basis, since the necessary storage stability is lacking.

The object of the present invention was to provide aqueous pesticide formulations containing the active ingredients Aclonifen and Flufenacet, free from

Tristyrolphenolethoxylaten (TSP-EO) are, have a sufficiently good biological activity and have a sufficient storage stability, with negative effects such as flocculation,

Sedimentation, agglomeration and crystal growth no longer occur.

This object is achieved by aqueous dispersions containing the active ingredients Aclonifen and Flufenacet and a mixture consisting of anionic surfactants from the group of

 Naphthalenesulfonate or from the group of condensation products of naphthalenesulfonates with formaldehyde, nonionic surfactants from the group of di- and tri-block copolymers

Alkylene oxides as a substitute for Tristyrolphenolethoxylaten (TSP-EO), a specific

Thickener mixture of at least one organic thickener based on xanthan gum and at least one inorganic thickener, preferably based on a synthetic thickener from the series of silicic acids, other agrochemical active compounds, preferably diflufenican, which may optionally be added further conventional auxiliaries and additives. The present invention thus relates to aqueous dispersions containing

a) the herbicidal active substances Aclonifen and Flufenacet,

b) one or more anionic surfactants from the group of the sulfonates selected from the groups based on the naphthalene, the alkylaryl, the condensed naphthalenes and based on lignin, c) one or more nonionic surfactants from the group of di- and tri- block copolymers of alkylene oxides,

d) an organic thickener based on xanthan,

e) an inorganic thickener,

f) optionally one or more agrochemical active ingredients other than component a), preferably the herbicidal active ingredient diflufenican,

g) optionally one or more other customary auxiliaries and additives,

and

 Water;

wherein the components d) and e) are present in specific mixing ratios to each other.

The dispersions of the invention show excellent storage stability. you are at

Room temperature stable for at least 2 years and show no unwanted effects, such. Crystal growth.

In a preferred embodiment, these dispersions contain

a) 20 to 45% of aclonifen and 4 to 20% of flufenacet, with a total amount of 24 to 65%, b) 0.3 to 3% of one or more anionic surfactants from the group of sulfonates selected from the groups based on naphthalene , the alkylaryl, the condensed naphthalenes and lignin-based,

c) 2 to 15% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.01 to 1% of an organic thickener based on xanthan,

e) 0.1 to 3% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active substances, preferably 1 to 12% diflufenican,

g) 0 to 20% of one or more other customary auxiliaries and additives,

and

 20 to 70% water;

wherein the components d) and e) are present in a ratio of 1: 300 to 10: 1 to each other.

A particularly preferred embodiment are dispersions according to the invention which contain a) 20 to 45% aclonifen and 4 to 20% flufenacet,

b) 0.3 to 3% of one or more anionic surfactants from the group of naphthalenesulfonates, alkylarylsulfonates or ligninsulfonates, as well as the group of condensation products of naphthalenesulfonates with formaldehyde,

c) 2 to 10% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.05 to 0.5% of an organic thickener based on xanthan,

e) 0.3 to 1.5% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active substances, preferably 1 to 12% diflufenican,

g) 0 to 20% of one or more other customary auxiliaries and additives,

and

 20 to 70% water;

wherein the components d) and e) are present in a ratio of 1: 30 to 2: 1-1.5 to each other.

A very particularly preferred embodiment are dispersions according to the invention which contain

a) 24 to 39% aclonifen and 6 to 14% flufenacet,

b) 0.4 to 2.5% of one or more anionic surfactants from the group of naphthalenesulionates, alkylarylsulphonates or ligninsulphonates, as well as the group of condensation products of

Naphthalenesulfonates with formaldehyde,

c) 2.5 to 8% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.1 to 0.3% of an organic thickener based on xanthan,

e) 0.4 to 1.3% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active substances, preferably 2 to 10% diflufenican,

g) 0 to 20% of one or more other customary auxiliaries and additives,

and

25 to 70% water;

wherein the components d) and e) are present in a ratio of 1:15 to 1: 1 to each other.

All percentages here and throughout the specification are percentages by weight (% by weight) and, unless otherwise defined, refer to the relative weight of the particular component based on the total weight of the formulation The herbicidal active compounds (components a) aclonifen (10) and flufenacet (397) as individual substances or as a mixture are known, for example, from "The Pesticide Manual", 16th edition (2012), The British Crop Protection Council (note: directory number in brackets) ,

 The proportion of these active ingredients in the dispersions according to the invention (component a) can be 0.1-50% by weight, preferably 20-45% by weight, more preferably 24-39% by weight for aclonifen and 0.1-50% by weight for flufenacet .-, preferably 4 to 20 parts by weight, particularly preferably 6 to 14 parts by weight. Proportionally, the total amount of both active ingredients can be between 24-65% by weight, preferably 25-55% by weight, particularly preferably 30-50% by weight. Examples of anionic surfactants (components b) from the group of naphthalenesulfonates are

Galoryl® MT 800 (sodium dibutylnaphthalenesulfonate), Morwet® IP (diisopropylnaphthalenesulfonate), and Nekal® BX (alkylnaphthalenesulfonate). Examples of anionic surfactants b) from the group of condensation products of naphthalenesulfonates with formaldehyde are Galoryl® DT 201

(Naphthalenesulfonic acid hydroxypolymer with formaldeyde and methylphenol sodium salt), Galoryl® DT 250 (condensation product of phenol and naphthalene sulfonates), Reserve® C

 (Condensation product of phenol and naphthalenesulfonates), Morwet® D-425 (Akzo-Nobel) and Tersperse® D-2020 (Huntsman) as each Naphthalinsulfonaten-formaldehyde condensate. Preference is given to unsubstituted naphthalenesulfonate formaldehyde condensates, such as e.g. Products Morwet® D-425. Examples of lignin-based are, for example, available calcium, potassium, ammonium or sodium lignin sulfonates such as Reax® 88, Kraftsperse® 25S (Westvaco) and Borresperse® types

 (Borregard). Very particular preference is given to condensation products based on naphthalenesulfonate. The proportion of anionic surfactants in the dispersions according to the invention (component b) can be from 0.3 to 3% by weight, preferably from 0.3 to 2.5% by weight, particularly preferably from 0.4 to 2.5% by weight. be. Examples of nonionic surfactants (components c) from the group of di- and tri-block copolymers of alkylene oxides include Suitable compounds based on ethylene oxide and propylene oxide having average molecular weights of between 200 and 10,000, preferably between 1000 and 4000 g / mol, the mass fraction of the polyethoxylated block varying between 10 and 80%, e.g.

Synperonic® PE series (Uniqema), Pluronic® PE series (BASF, such as Pluronic® PE 10500), VOP® 32 or Genapol® PF series (Clariant), the products of said series being preferred.

The proportion of nonionic surfactants in the dispersions according to the invention (component c) can be from 2 to 15% by weight, preferably from 2 to 10% by weight, particularly preferably from 2.5 to 8% by weight.

The components b) and c) according to the invention enable the exchange of

Tristyrolphenolethoxylaten (TSP-EO), which are generally both anionic and non-ionic. A typical anionic representative is Soprophor® FLK (Solvay), a typical non-ionic representative is Soprophor® BSU (Solvay). Suitable organic thickeners (components d) are organic natural or biotechnologically modified or organically synthetic thickeners. Typical synthetic thickeners are from the Rheostrux® (Croda), Thixin® or Thixatrol® series (Elementis). These are typically based on acrylates. Typical organic thickeners are based on xanthan or cellulose or a combination thereof. Preference is given to using natural modified thickeners based on xanthan. Typical representatives are for example Rhodopol® (Solvay) and Kelzan® (Kelco Corp.) as well as Satiaxane® (Cargill).

 The proportion of organic thickeners in the dispersions (component d) according to the invention can be up to 5% by weight, preferably 0.01-1.0% by weight, particularly preferably 0.01-0.6% by weight, very particularly preferably 0, 05-0.5% by weight and especially preferably 0.1-0.3% by weight.

Examples of inorganic thickeners (components e) are:

 1) modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel®

 (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel), or the Van Gel® series (R.T. Vanderbilt),

 2) synthetic silicic acids and their derivatives, such as silicates of the Sipernat®, Aerosil® or Durosil® series (Degussa), the CAB-0-SIL® series (Cabot). Silica is preferred. The proportion of inorganic thickeners in the dispersions (component e) according to the invention can be up to 5% by weight, preferably 0.1-3% by weight, more preferably 0.2-1.5% by weight, very particularly preferably 0, 3 to 1.5% by weight and more preferably 0.4 to 1.3% by weight.

According to the invention, the specific mixture of organic thickeners d) and inorganic thickeners e), which are present in the following proportions to each other:

 (Component d): (Component e)

 in general (1: 300) - (10: 1),

 preferably (1: 150) - (3: 1-1.5),

 more preferably (1:30) - (2: 1-1,5),

 most preferably (1: 15) - (1: 1).

As optionally added, of component a) different agrochemical active ingredients

(Components f) are suitable herbicides, fungicides, insecticides, plant growth regulators, safeners and the like. These active ingredients are known, for example, from "The Pesticide Manual", 16th Edition (2012, The British Crop Protection Council (Note: Directory number in brackets) Preferably, the herbicidal active ingredient diflufenican (272). The fraction of optionally added component (a) of various agrochemical active ingredients in the dispersions of the invention (component f) may be up to 50% by weight, preferably up to 40% by weight, more preferably up to 30% by weight. In the case of the herbicidal active ingredient diflufenican, the proportion may be 0.1-50% by weight, preferably 1-12% by weight, more preferably 2-10% by weight.

The optionally added further customary auxiliaries and additives (component g) are, for example, defoamers, antifreeze agents, structure-forming substances, preservatives, antioxidants, dyes and fragrances, wetting, anti-drift, adhesion and penetration agents (adjuvants), fertilizers, and other from the components b) and c) different surfactants.

Suitable defoamers are silicone-based or silane-based surface-active compounds such as the Tegopren® products (Goldschmidt), the SE® products (Wacker), and the Bevaloid®, and

Silcolapse® products (Solvay, Dow Corning, Reliance, GE, Bayer). Preference is given to SE® (Wacker), Rhodorsil® products (Bluestar Silicones) and particular preference is given, for example, to Products like Silcolapse® 5020.

 Suitable antifreeze agents are those from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol, preferably propylene glycol.

 Suitable preservatives are e.g. Products such as Acticide® MBS (biocide, Thor chemistry).

Suitable antioxidants, dyes and fragrances, wetting, anti-drift, adhesive and penetration agents (adjuvants) and fertilizers are known to the person skilled in the art.

 Suitable further of the components b) and c) different surfactants are, for example

Emulsifiers, wetting agents and dispersants.

As emulsifiers, wetting agents and dispersing agents are e.g. nonionic emulsifiers and

Dispersants in question, for example:

 1) polyalkoxylated, preferably polyethoxylated, saturated and unsaturated aliphatic alcohols,

with 8 to 24 carbon atoms in the alkyl radical, which is derived from the corresponding fatty acids or from petrochemical products, and

 - With 1 to 100, preferably 2 to 50, ethylene oxide units (EO), wherein the free hydroxyl group is optionally alkoxylated, and

 - the e.g. commercially available as Genapol® X and Genapol® O series (Clariant), Crovol® M series (Croda) or Lutensol® series (BASF);

 2) polyalkoxylated, preferably polyethoxylated hydroxyfatty acids or hydroxyfatty acids containing glycerides, e.g. Ricinin or castor oil, with a degree of ethoxylation between 10 and 80, preferably 25 to 40, such. Emuisogen® EL series (Clariant) or Agnique® CSO series

(BASF); 3) polyalkoxylated, preferably polyethoxylated sorbitan esters, such as Atplus® 309 F (Croda) or

Alkamuls® series (Solvay).

Preferred nonionic emulsifiers and dispersants are e.g. polyethoxylated alcohols and polyethoxylated triglycerides containing hydroxy fatty acids.

Also suitable are ionic emulsifiers and dispersants, for example:

 1) polyalkoxylated, preferably polyethoxylated emulsifiers / dispersants which are ionically modified, e.g. by reacting the terminal free hydroxyl function of the polyethylene oxide block to form a sulfate or phosphate ester (e.g., alkali and alkaline earth metal salts), e.g. Genapol® LRO or Dispersant 3618 (Clariant), Emulphor® (BASF) or Crafol® AP (Cognis);

 2) Alkali and alkaline earth metal salts of linear or branched alkyl chain alkylaryl sulfonic acids such as phenyl sulfonate CA or phenyl sulfonate CAL (Clariant), Atlox® 3377BM (Croda), Empiphos® ™ series (Huntsman);

 3) Polyelectrolytes, such as polystyrene sulfonate or sulfonated unsaturated or aromatic polymers (polystyrenes, polybutadienes or polyterpenes)

 The proportion of optionally added further customary auxiliaries and additives in the

dispersions according to the invention (component g) can be up to 20% by weight, preferably up to 15% by weight. The proportion of the component water in the dispersions according to the invention can be from 20 to 70% by weight, preferably from 20 to 60% by weight, particularly preferably from 30 to 55% by weight, very particularly preferably from 25 to 45% by weight.

The above-mentioned formulation auxiliaries of components b), c), d), e) and g) are known to the person skilled in the art and / or are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd Ed., Darland Books , Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed.,

Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Athylenoxidaddukte", Wiss. Publishing company, Stuttgart 1976; Winnacker-Kuchler, "Chemical Technology", Volume 7, 4th ed., C. Hanser Verlag, Munich 1986.

For use, the dispersions of the invention can be diluted in a customary manner, for example by means of water. It may be advantageous to the spray mixtures obtained further agrochemical active ingredients (eg tank mix partners in the form of appropriate formulations) and / or customary auxiliaries and additives, for example self-emulsifying oils such as vegetable oils or paraffin oils and / or Add fertilizer. The present invention therefore also relates to those herbicidal compositions which can be prepared on the basis of the dispersions of the invention.

These herbicidal compositions prepared on the basis of the dispersions according to the invention, also referred to below as herbicidal compositions according to the invention, have an excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Also difficult to control perennial weeds, from rhizomes, rhizomes or others

Cast out permanent organs are well recorded. The means may e.g. be applied in pre-sowing, pre-emergence or post-emergence. Specifically, some representatives of the monocotyledonous and dicotyledonous weed flora may be mentioned, which can be controlled by the herbicidal compositions according to the invention, without any restriction being made to certain species by the mention

 On the side of the monocotyledonous weeds, e.g. Apera spica venti, Avena spp., Alopecurus spp. (such as Alopecurus myosuroides, syn .: Arableweed, ALOMY), Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and Bromus spp. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperusarten from the annuelle group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten well.

In dicotyledonous weed species, the spectrum of activity extends to species such as e.g. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, as well as Convolvulus, Cirsium, Rumex, and Artemisia in perennial weeds. Under the specific culture conditions occurring in rice harmful plants such. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the agents according to the invention.

If the herbicidal compositions according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die completely after three to four weeks.

When the herbicidal compositions according to the invention are applied to the green plant parts in

Postemergence also occurs very rapidly after treatment, a drastic halt in growth and the weed plants remain in the existing at the time of application growth stage stand or die completely after a certain time, so that in this way a weed competition harmful to crops is eliminated very early and sustainably.

The herbicidal compositions according to the invention are distinguished by a rapidly onset and long-lasting herbicidal action. The rainfastness of the active ingredients in the combinations according to the invention is generally favorable. A particular advantage is the fact that the effective and used in herbicidal compositions dosages of herbicidal compounds can be set so low that their soil effect is optimally low. Thus, their use is not only possible in sensitive cultures, but groundwater contaminations are virtually avoided. The inventive combination of active ingredients is a considerable

Reduction of the necessary application rate of the active ingredients allows

 The said properties and advantages are useful in the practical weed control in order to keep agricultural crops free from undesired competing plants and thus to secure and / or increase the yields qualitatively and quantitatively. The technical standard is significantly exceeded by these new means in terms of the properties described.

Although the herbicidal compositions have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops, e.g.

dicotyledonous crops such as soybean, cotton, oilseed rape, sugarbeet, or graminaceous crops such as wheat, barley, rye, oats, millet, rice or maize, only marginally or not at all damaged. For these reasons, the herbicidal compositions according to the invention are very well suited for the selective

Control of undesirable plants grew in agricultural crops or in ornamental plantings. In addition, the herbicidal compositions of the present invention are excellent

growth regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to influence the metabolism

Phytochemicals and to facilitate harvesting, e.g. be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. A

Inhibition of vegetative growth plays a major role in many monocotyledonous and dicotyledonous cultures, as it can reduce or completely prevent storage.

On account of their herbicidal and plant growth-regulating properties, the herbicidal compositions according to the invention can also be employed for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example, by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.

Preferred is the use of the herbicidal agents of the invention in economically important transgenic crops of useful and ornamental plants, e.g. graminaceous crops such as wheat, barley, rye, oats, millet, rice and maize, as well as cultures of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables. Preferably, the agents according to the invention can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant. In the application of the herbicidal compositions according to the invention in transgenic crops, in addition to the effects observed in other crops against harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be combated. modified application rates that can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crops.

The present invention further provides a method for controlling unwanted plants grew, preferably in crops such as cereals (eg wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, oilseed rape, cotton and soybeans, particularly preferred in monocotyledonous crops such as cereals, eg Wheat, barley, rye, oats, crosses thereof, such as triticale, rice, corn and millet, wherein one or more herbicidal agents of the invention are grown on the harmful plants, plant parts, plant seeds or the area on which the plants grow, e.g. applied the acreage

The plant cultures may also be genetically engineered or obtained by mutation selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors.

Preference is given to using the herbicidal compositions according to the invention in preemergence and postemergence, particularly preferably in preemergence, very particularly preferably in preemergence in sown

Winter cereals (as part of an autumn application)

In addition, other particular embodiments of the aqueous dispersions and herbicidal compositions of the invention are disclosed in the claims. The preparation of the dispersions according to the invention can be carried out by methods known to the person skilled in the art; for example according to Houben-Weil by wet grinding by means of a bead mill (see:

Winnacker-Kuchler, "Chemische Technologie", Volume 7, 4th ed., C. Hanser Verlag, Munich 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y. 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed., G. Goodwin Ltd., London 1979). The advantage here is optionally a uniform particle distribution of the active substances in question, in addition to further prevent crystal growth and flocculation.

The following table gives examples of aqueous dispersions according to the invention. The terms used in the following examples have the following meanings:

Aclonifen Common name (BSI, pa ISO); IUPAC name: 2-chloro-6-nitro-3-phenoxyaniline (Bayer CropScience AG)

 Flufenacet Common name (BSI, pa ISO); IUPAC name: 4'-fluoro-N-isopropyl-2- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yloxy) acetanilide (Bayer

 CropScience AG)

 Diflufenican common name (BSI, draft E-ISO, (m) draft F-ISO); IUPAC name: 2 ', 4'-difluoro-2- (a, a, a-trifluoro-m-tolyloxy) nicotinanilide (Bayer

 CropScience AG)

 Morwet® D-425 naphthalenesulfonic acid formaldehyde condensate, sodium salt (Akzo

 Nobel)

 Pluronic® PE 10500 = polypropylene oxide-polyethylene oxide (PO-EO) block polymer, non-ionic

 (BASF)

 TSP-EO surfactant group: Tristyrolphenolethoxylate

 Soprophor® FLK representative of the TSP-EO group: ethoxylated (16 EO) tristyrylphenol phosphate, potassium salt, anionic (Solvay)

 Soprophor® BSU Representative of the TSP-EO Group: Ethoxylated (16 EO) tristyrylphenol, non-ionic (Solvay)

 Rhodopol® G Xanthan derivative, organic thickener (Solvay)

 Aerosil® 200 Pyrogenic Silica, Inorganic Thickener (Evonik)

 Citric acid polybasic organic acid

 Silcolapse® 411 Silicone Defoamer (Bluestar Silicones)

Glycerin antifreeze

Proxel® GXL preservative (biocide, Arch) 1. Preparation of the aqueous dispersions

For the preparation of the examples given in Table 1, initially water is introduced. Aclonifen and flufenacet (component a) (and optionally further active compounds (component f)) and the further components b), c), e) and g) are then added with stirring (without special order). Subsequently, a wet grinding takes place for example by means of a bead mill.

Finally, the organic thickener (component d) is added.

Table 1: Compositions (% by weight,% by weight)

 Explanation of the comparative examples:

 - VI = Modified formulation based on the commercial Bandur 600 SC formulation containing TSP-EO and the components d) and e) - the modification comprises in each case the addition of the components a) and f) in view of the better comparability with the inventive examples ;

- V2 + V3 = formulations without the specific thickener combination of components d) and e) - analogously to the composition of Example 2 according to the invention. 2. Storage stability and further formulation properties of the aqueous dispersions

The novel dispersions of Examples 1 to 7 have excellent storage stability. They are stable at room temperature for at least 2 years and at 40 ° C for at least 3 months without negative changes. In Table 2, the examples of the invention with the not

Comparative examples of the invention are compared from Table 1.

Procedure: All tests were carried out according to CIPAC methods commonly used in plant protection (CIPAC = Collaborative International Pesticides Analytical Council, www.cipac.org). The

Long-term storage was carried out according to CIPAC MT 46.3 at 8 weeks 40 ° C storage time. The following terms have the following meaning:

 - OTW = test result after zero days of storage.

 - 8W40 = accelerated storage test result (8 weeks 40 ° C) to verify the long-term stability of a formulation product.

- Suspensibility = distribution of active ingredient in a 1% aqueous solution (100% = completely homogeneously distributed, 0% = completely sedimented);

 - Suspensibility 8W40 = distribution of active ingredient after storage test (8 weeks 40 ° C); Values <100% lead to inconsistent product distribution after application; according to international requirements, formulation products must have values> 60% D90 = active ingredient particle size (laser scattering 90% of all volume particles).

 - D90 8W40 = active ingredient particle size after storage test (8 weeks 40 ° C); elevated values indicate crystal growth, with increases by a factor of 2 being considered acceptable while

 Increases by a factor of 4 are no longer acceptable. Sediment = values> 10% indicate strong sediment formation.

- Shake up sediment = Yes for acceptable; No for unusable formulation products, because active ingredients can no longer be transferred to a spray mixture.

- wet sieving = measure of possible filter blockages in the spray application; Values> 0.1% to 150 μιη sieve and> 0.2% to 45 μιη sieve (in each case based on the amount of formulation used) are not acceptable. Table 2: Storage stability and further formulation properties - Comparison Example 2 (according to the invention) with Comparative Examples V1-V3 (not according to the invention)

Comment: The storage stability experiments show that only example 2 (containing the

 inventive thickener mixture of component d), here Rhodopol® G, and component e), here Aerosil® 200, in conjunction with the active ingredient mixture a) or f), component b), here Morwet® D-425, and Component c), here Pluronic® PE 10500), over the desired

 Formulation properties, such as storage stability.

Comparative Example VI (containing TSP-EO) which is not according to the invention is not storage-stable and shows crystal growth. Comparative Examples C2 and V3 (without thickener mixture according to the invention) show high sediment formation leading to unusable formulations Inventive Examples 1, 3 to 7 from Table 1 have the same desired formulation properties as Example 2. 3. Herbicidal activity of the aqueous dispersions

Procedure: Standard autumn field application of 200L / ha spray mixtures with the dosage of 600 g Aclonifen, 240 g Flufenacet and 120 g Diflufenican per hectare. The herbicidal activity was evaluated on the field foxtail (Alopecurus myosuroides, ALOMY) and the phytotoxicity on the crops winter barley and winter wheat; rated visually as compared to an untreated control group according to a scale of 0-100%: 0% = no detectable effect compared to the untreated control group; 100% = complete effect compared to the untreated control group.

Table 3: Comparative experiment: (tank mix vs. co-formulation)

 Used commercial products:

 Bandur = Bandur 600 SC formulation containing 600 g / L aclonifen (50% by weight) and TSP-EO (Bayer CropScience AG)

 Cadou = Cadou 508 SC formulation containing 508 g / L of flufenacet (42% by weight) and

 Component c): Pluronic PE 10500 (Bayer CropScience AG)

 - Brodal = Brodal 500 SC formulation containing 500 g / L diflufenican (42 wt .-%) and TSP-EO (Bayer CropScience AG) Comment: The co-formulation of the invention with the herbicidal active ingredients (Example 7) without TSP-EO shows not only a higher herbicidal efficacy than the comparable tank mix (92% vs. 88%) but also causes a lower phytotoxicity on the crops winter barley (12% vs. 18%) and winter wheat (2% vs. 5%).

 This comparative experiment demonstrates that the co-formulation according to the invention of the herbicidal

 Active ingredients is more advantageous than the corresponding tank mix of individually formulated active ingredients.

Claims

Claims:

1. Aqueous dispersions containing

a) the herbicidal active substances Aclonifen and Flufenacet,

b) one or more anionic surfactants from the group of the sulfonates selected from the groups based on the naphthalene, the alkylaryl, the condensed naphthalenes and based on lignin, c) one or more nonionic surfactants from the group of di- and tri- block copolymers from

 alkylene oxides,

d) an organic thickener based on xanthan,

e) an inorganic thickener,

f) optionally one or more agrochemical active ingredients which differ from component a), g) if appropriate one or more further customary auxiliaries and additives,

and

 Water;

wherein the components d) and e) are present in specific mixing ratios to each other.

2. dispersions according to claim 1 containing

a) 20 to 45% of aclonifen and 4 to 20% of flufenacet, with a total amount of 24 to 65%, b) 0.3 to 3% of one or more anionic surfactants from the group of sulfonates selected from the groups based on naphthalene , the alkylaryl, the condensed naphthalenes and lignin-based,

c) 2 to 15% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.01 to 1% of an organic thickener based on xanthan,

e) 0.1 to 3% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active ingredients, g) 0 to

20% of one or more other common auxiliaries and additives,

and

 20 to 70% water;

wherein the components d) and e) are present in a ratio of 1: 300 to 10: 1 to each other.

3. Dispersions according to claim 1, comprising

a) 20 to 45% aclonifen and 4 to 20% flufenacet,

b) 0.3 to 3% of one or more anionic surfactants from the group of naphthalenesulfonates,

 Alkylarylsulfonate or lignosulfonates, and the group of condensation products of

Naphthalenesulfonates with formaldehyde, c) 2 to 10% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.05 to 0.5% of an organic thickener based on xanthan,

e) 0.3 to 1.5% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active ingredients, g) 0 to 20% of one or more further customary auxiliaries and additives,

and

 20 to 70% water;

wherein the components d) and e) are present in a ratio of 1: 30 to 2: 1-1.5 to each other.

4. Dispersions according to claim 1, comprising

a) 24 to 39% aclonifen and 6 to 14% flufenacet,

b) from 0.4 to 2.5% of one or more anionic surfactants from the group of naphthalenesulfonates,

 Alkylarylsulfonate or lignosulfonates, and the group of condensation products of

 Naphthalenesulfonates with formaldehyde,

c) 2.5 to 8% of one or more nonionic surfactants from the group of di- and tri-block copolymers of alkylene oxides,

d) 0.1 to 0.3% of an organic thickener based on xanthan,

e) 0.4 to 1.3% of an inorganic thickener,

f) 0 to 50% of one or more of component a) of various agrochemical active ingredients, g) 0 to 20% of one or more further customary auxiliaries and additives,

and

 25 to 70% water;

wherein the components d) and e) are present in a ratio of 1:15 to 1: 1 to each other.

5. Dispersions according to any one of claims 1 to 4, wherein the different from a) agrochemical active substance is diflufenican (component f).

6. Dispersions according to one or more of claims 1 to 5, additionally containing one or more further customary auxiliaries and additives (component g) such as defoamers,

Antifreeze, structure-forming substances, preservatives, antioxidants, dyes and fragrances, wetting, anti-drift, adhesion and penetration agents (adjuvants) and fertilizers.

7. A process for the preparation of an aqueous dispersion according to one or more of

Claims 1 to 6, wherein the components a), b), c), e), g) and optionally f) mixed and then ground and finally component d) is added.

A method of controlling undesired plants wherein an effective amount of an aqueous dispersion according to one or more of claims 1 to 6 is applied to the plants, parts of the plants, the seed or the area growing on the plant.

9. Use of an aqueous dispersion according to one or more of claims 1 to 6, for controlling unwanted plants grew.

10. Use of an aqueous dispersion according to one or more of claims 1 to 6, for the preparation of a herbicidal composition.

11. Use according to claim 10, wherein the herbicidal agent is a suspension or

Suspoemulsion is.

12. A liquid herbicidal composition obtainable by diluting an aqueous dispersion according to one or more of claims 1 to 6.

A liquid herbicidal composition according to claim 12, wherein the herbicidal agent is an emulsion, suspension, suspoemulsion or solution.

14. A liquid herbicidal composition according to one or more of claims 12 and 13, comprising

a) the herbicidal active substances Aclonifen and Flufenacet,

b) one or more anionic surfactants from the group of the sulfonates selected from the groups based on the naphthalene, the alkylaryl, the condensed naphthalenes and based on lignin, c) one or more nonionic surfactants from the group of di- and tri- block copolymers from

 alkylene oxides,

d) an organic thickener based on xanthan,

e) an inorganic thickener,

and

Water;

wherein the components d) and e) are present in specific mixing ratios to each other.

15. A liquid herbicidal composition according to claim 14, additionally containing

f) one or more agrochemical active ingredients that differ from component a),

g) one or more further customary auxiliaries and additives.

A liquid herbicidal composition according to claim 15, wherein the agrochemical active ingredient other than component a) is diflufenican.

17. A method for controlling unwanted plants grew, wherein an effective amount of a herbicidal composition according to one or more of claims 12 to 16 to the plants, parts of the plants, the seed or the area grow on the plant is applied.

18. Use of a herbicidal composition according to one or more of claims 12 to 16, for controlling unwanted plants grew.

19. Use of a herbicidal composition according to one or more of claims 12 to 16, for controlling undesired plant growth in pre-emergence and post-emergence,